JP3510740B2 - Manufacturing method of integrated thin-film solar cell - Google Patents

Manufacturing method of integrated thin-film solar cell

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Publication number
JP3510740B2
JP3510740B2 JP22347296A JP22347296A JP3510740B2 JP 3510740 B2 JP3510740 B2 JP 3510740B2 JP 22347296 A JP22347296 A JP 22347296A JP 22347296 A JP22347296 A JP 22347296A JP 3510740 B2 JP3510740 B2 JP 3510740B2
Authority
JP
Japan
Prior art keywords
layer
film
back electrode
photoelectric conversion
electrode layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP22347296A
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Japanese (ja)
Other versions
JPH1070295A (en
Inventor
晋 木戸口
哲正 梅本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sharp Corp
Original Assignee
Sharp Corp
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Filing date
Publication date
Application filed by Sharp Corp filed Critical Sharp Corp
Priority to JP22347296A priority Critical patent/JP3510740B2/en
Priority to US08/917,105 priority patent/US5956572A/en
Priority to EP97306507A priority patent/EP0827212B1/en
Priority to DE69734860T priority patent/DE69734860T2/en
Publication of JPH1070295A publication Critical patent/JPH1070295A/en
Application granted granted Critical
Publication of JP3510740B2 publication Critical patent/JP3510740B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/362—Laser etching
    • B23K26/364—Laser etching for making a groove or trench, e.g. for scribing a break initiation groove
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/40—Removing material taking account of the properties of the material involved
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03921—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including only elements of Group IV of the Periodic System
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
    • H01L31/046—PV modules composed of a plurality of thin film solar cells deposited on the same substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
    • H01L31/046—PV modules composed of a plurality of thin film solar cells deposited on the same substrate
    • H01L31/0463—PV modules composed of a plurality of thin film solar cells deposited on the same substrate characterised by special patterning methods to connect the PV cells in a module, e.g. laser cutting of the conductive or active layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/056—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means the light-reflecting means being of the back surface reflector [BSR] type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
    • H01L31/202—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic System
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/16—Composite materials, e.g. fibre reinforced
    • B23K2103/166—Multilayered materials
    • B23K2103/172—Multilayered materials wherein at least one of the layers is non-metallic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S438/00—Semiconductor device manufacturing: process
    • Y10S438/94—Laser ablative material removal

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は集積型薄膜太陽電池
の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for manufacturing an integrated type thin film solar cell.

【０００２】[0002]

【従来の技術】絶縁表面を有する透光性基板上に非晶質
半導体光電変換層が設けられた薄膜太陽電池は、集積型
の構造を用いることにより、所定の電圧を比較的容易に
取り出すことができる。従来の集積型薄膜太陽電池の製
造方法は、例えば特開昭６３−３４７０号公報に記載さ
れているように、薄膜の形成とそのスクライブを繰り返
しながら製造するものである。この従来の集積型薄膜太
陽電池の製造方法を図４を用いて説明する。2. Description of the Related Art A thin film solar cell in which an amorphous semiconductor photoelectric conversion layer is provided on a light-transmitting substrate having an insulating surface can extract a predetermined voltage relatively easily by using an integrated type structure. You can A conventional method for manufacturing an integrated thin-film solar cell is, for example, as described in Japanese Patent Laid-Open No. 63-3470, a method of manufacturing a thin film by repeating formation of the thin film and scribing thereof. A method of manufacturing the conventional integrated thin film solar cell will be described with reference to FIG.

【０００３】まず、図４（ａ）に示すように、ガラス基
板のような絶縁表面を有する透光性基板１の表面上に透
明導電膜層３を蒸着法、ＣＶＤ（Chemical Vapor Depos
ition）法やスパッタリング法を使用して成膜し、透明
導電膜電極とする。そして、レーザスクライブ法により
レーザ光１１を照射し、透明導電膜層３を短冊状に分割
加工して各セル間を絶縁する。これを第１のスクライブ
という。また、第１のスクライブにより生じた溝を第１
のスクライブラインという。このように、基板１の表面
上に短冊状に透明導電膜層３が設けられる。First, as shown in FIG. 4A, a transparent conductive film layer 3 is deposited on the surface of a transparent substrate 1 having an insulating surface such as a glass substrate by a vapor deposition method, a CVD (Chemical Vapor Depos) method.
ition) method or sputtering method to form a film, which is used as a transparent conductive film electrode. Then, the laser light 11 is irradiated by the laser scribing method to divide the transparent conductive film layer 3 into strips to insulate each cell. This is called the first scribe. In addition, the groove formed by the first scribe
Scribe line. Thus, the strip-shaped transparent conductive film layer 3 is provided on the surface of the substrate 1.

【０００４】次に、図４（ｂ）に示すように基板１の表
面上に非晶質半導体光電変換層４をＣＶＤ法等で積層す
る。光電変換層４を第１のスクライブと平行で近接した
位置において、透明導電膜層３を損傷させることなく、
レーザスクライブ法によりレーザ光１２を照射して開溝
除去する。これを第２のスクライブという。また、第２
のスクライブにより生じた溝を第２のスクライブライン
という。このように、図４（ｂ）に示すように光電変換
層４が分割される。Next, as shown in FIG. 4B, an amorphous semiconductor photoelectric conversion layer 4 is laminated on the surface of the substrate 1 by a CVD method or the like. At the position where the photoelectric conversion layer 4 is parallel and close to the first scribe, without damaging the transparent conductive film layer 3,
The laser beam 12 is irradiated by the laser scribing method to remove the open groove. This is called the second scribe. Also, the second
The groove created by the scribe is called a second scribe line. In this way, the photoelectric conversion layer 4 is divided as shown in FIG.

【０００５】更に、図４（ｃ）に示すように光電変換層
４と第２のスクライブライン上に裏面電極層１０を積層
する。その後、レーザスクライブ法により、第２のスク
ライブラインと平行で近接した位置で、第２のスクライ
ブラインに対して第１のスクライブラインを挟む位置に
おいて、裏面電極層１０を開溝除去する。これを第３の
スクライブという。また、第３のスクライブにより生じ
た溝を第３のスクライブラインという。Further, as shown in FIG. 4C , a back electrode layer 10 is laminated on the photoelectric conversion layer 4 and the second scribe line. After that, the back surface electrode layer 10 is removed by the laser scribing method at a position parallel to and close to the second scribe line and at a position sandwiching the first scribe line with respect to the second scribe line. This is called the third scribe. Further, the groove formed by the third scribe is called a third scribe line.

【０００６】また、第３のスクライブにおいて、レーザ
スクライブ法によって裏面電極層１０を直接、開溝除去
する方法の他に、図４（ｄ）に示すように印刷法によっ
てレジストを塗布してレジスト膜７を設け、その際にパ
ターニングを施して、図４（ｅ）に示すようにエッチン
グ液によって裏面電極層１０を溶解除去する方法、或い
はメタルマスクによって蒸着法やスパッタリング法で裏
面電極層１０の形成と同時に絶縁分割を行う方法があ
る。このように、第３のスクライブにより短冊状にセル
が分割され、ユニットセルが直列接続される。Further, in the third scribing, in addition to the method of directly removing the open groove of the back electrode layer 10 by the laser scribing method, as shown in FIG. 4D, a resist is applied by a printing method to form a resist film. 7 is provided, patterning is performed at that time, and the back electrode layer 10 is dissolved and removed by an etching solution as shown in FIG. 4E, or the back electrode layer 10 is formed by vapor deposition or sputtering with a metal mask. At the same time, there is a method of performing insulation division. In this way, the cells are divided into strips by the third scribe, and the unit cells are connected in series.

【０００７】尚、第３のスクライブにおいてレーザスク
ライブ法による加工では、第２のスクライブラインと第
３のスクライブラインの間隔が小さくできるため、集積
セル全体の発電有効面積損失を低減することができる。In the third scribing process by the laser scribing method, the distance between the second scribing line and the third scribing line can be made small, so that the power generation effective area loss of the entire integrated cell can be reduced.

【０００８】[0008]

【発明が解決しようとする課題】しかし、レーザスクラ
イブ法による加工により、裏面電極層１０のみを選択的
に開溝除去するとき、照射するレーザ光の影響により非
晶質半導体光電変換層４の表面部が結晶化して比抵抗が
低下する。そのため、リークが発生する原因となる。ま
た、裏面電極層１０と光電変換層４をレーザスクライブ
法により一括して開溝除去することも可能であるが、そ
の場合には、スクライブによる裏面電極層１０の屑と透
明導電膜層３が短絡しやすい。そのため、漏れ電流が発
生する。このように、いずれの場合においてもシャント
抵抗が低下し、歩留まりが低下する要因となっていた。However, the surface of the amorphous semiconductor photoelectric conversion layer 4 is affected by the irradiation of the laser beam when only the back electrode layer 10 is selectively removed by the groove processing by the laser scribing method. The part is crystallized and the specific resistance is lowered. Therefore, it causes a leak. It is also possible to remove the grooves on the back surface electrode layer 10 and the photoelectric conversion layer 4 at once by a laser scribing method. In that case, scraps of the back surface electrode layer 10 due to the scribing and the transparent conductive film layer 3 are removed. Easy to short circuit. Therefore, a leakage current is generated. As described above, in any case, the shunt resistance was reduced, which was a factor of reducing the yield.

【０００９】また、裏面電極層１０の形成に前述した蒸
着法、スパッタリング法等を用いる場合、成膜時にメタ
ルマスクを使用することにより成膜と同時に裏面電極層
１０のパターニングを施すことも行われていた。しか
し、この場合、メタルマスクのエッジ部によって光電変
換層４が破損され、リークの発生や変換効率の低下の原
因となっていた。また、蒸着時に回り込みによるパター
ニングの不良が発生するのを防止するため、裏面電極層
１０の絶縁部幅を大きく取らざるを得ず、発電有効面積
損失が大きくなるという欠点を有していた。When the above-mentioned vapor deposition method, sputtering method or the like is used to form the back electrode layer 10, the back electrode layer 10 is patterned at the same time as the film formation by using a metal mask during the film formation. Was there. However, in this case, the photoelectric conversion layer 4 was damaged by the edge portion of the metal mask, causing a leak and a decrease in conversion efficiency. In addition, in order to prevent patterning defects due to wraparound during vapor deposition, the width of the insulating portion of the back electrode layer 10 must be increased, which results in a large power generation effective area loss.

【００１０】更に、裏面電極層１０にスクリーンマスク
等を使用してパターニング印刷でレジストを塗布し、エ
ッチング液で裏面電極層１０を溶解除去する方法は、確
実に裏面電極の分割ができるものの、印刷精度の限界か
ら集積モジュール全体の発電有効面積損失が大きくなっ
ていた。Further, the method of applying a resist to the back electrode layer 10 by patterning printing using a screen mask or the like and dissolving and removing the back electrode layer 10 with an etching solution can surely divide the back electrode, Due to the limit of accuracy, the effective power generation area loss of the entire integrated module was large.

【００１１】本発明は上記課題を解決し、非晶質半導体
光電変換層の膜質低下を防ぎ、集積化による発電有効面
積損失を低減する集積型薄膜太陽電池の製造方法を提供
することを目的とする。It is an object of the present invention to solve the above problems, and to provide a method for manufacturing an integrated type thin film solar cell, which prevents deterioration of the film quality of an amorphous semiconductor photoelectric conversion layer and reduces power generation effective area loss due to integration. To do.

【００１２】[0012]

【課題を解決するための手段】上記目的を達成するた
め、本発明では、絶縁表面を有する透光性基板上に透明
導電膜電極を設け、第1のスクライブにより前記透明導
電膜電極を分割し、次に非晶質半導体光電変換層を設
け、第2のスクライブにより前記非晶質半導体光電変換
層を分割し、更に裏面電極層を設け、第3のスクライブ
により前記裏面電極層を分割する集積型薄膜太陽電池の
製造方法において、前記裏面電極層は酸化亜鉛又はＩＴ
Ｏからなる透明導電膜と、銀からなる金属反射膜層の２
層からなり、前記第3のスクライブの際、前記裏面電極
層にレジストを塗布してレジスト膜を設けた後に、前記
非晶質半導体光電変換層に影響を及ぼさない、波長５３
２ｎｍのレーザ光照射により前記レジスト膜を開溝除去
し、前記２層からなる裏面電極層をエッチング液（ＳＣ
１）を用いて溶解除去するものとする。In order to achieve the above object, in the present invention, a transparent conductive film electrode is provided on a transparent substrate having an insulating surface, and the transparent conductive film electrode is divided by a first scribe. Next, an amorphous semiconductor photoelectric conversion layer is provided, the amorphous semiconductor photoelectric conversion layer is divided by a second scribe, a back electrode layer is further provided, and the back electrode layer is divided by a third scribe. In the method for manufacturing a thin film solar cell, the back electrode layer is zinc oxide or IT.
A transparent conductive film made of O and a metal reflective film layer made of silver.
Consist layer, when the third scribing, after providing a resist film by applying a resist on the back electrode layer, wherein
A wavelength of 53 which does not affect the amorphous semiconductor photoelectric conversion layer
The resist film is removed by irradiating with a laser beam of 2 nm, and the back electrode layer consisting of the two layers is etched with an etching solution (SC
It should be dissolved and removed using 1).

【００１３】この方法では、絶縁表面を有する透光性基
板上に透明導電膜電極が設けられる。そして第１のスク
ライブにより透明導電膜電極が分割される。次に非晶質
半導体光電変換層が設けられる。そして第２のスクライ
ブにより非晶質半導体光電変換層が分割される。更に透
明導電膜と金属反射膜層との２層構造の裏面電極層が設
けられる。裏面電極層にレジストが塗布されてレジスト
膜が設けられる。レーザ光の照射によりレジスト膜が開
溝除去される。そしてエッチング液により裏面電極層の
透明導電膜と金属反射膜層が溶解除去される。このよう
に、第３のスクライブが行われる。In this method, the transparent conductive film electrode is provided on the transparent substrate having the insulating surface. Then, the transparent conductive film electrode is divided by the first scribe. Next, an amorphous semiconductor photoelectric conversion layer is provided. Then, the amorphous semiconductor photoelectric conversion layer is divided by the second scribe. More transparent
A back electrode layer having a two-layer structure of a bright conductive film and a metal reflective film layer is provided. A resist is applied to the back electrode layer to form a resist film. More resist film irradiated with the laser beam is an open groove removed. And the back electrode layer
The transparent conductive film and the metal reflective film layer are dissolved and removed. In this way, the third scribe is performed.

【００１４】[0014]

【００１５】[0015]

【００１６】[0016]

【００１７】[0017]

【００１８】[0018]

【００１９】ここで、金属反射膜層は銀からなり、レー
ザ光の波長が４５０ｎｍ以上の領域では、その反射率は
９０％以上となる。そのため、レジスト膜の除去の際、
レーザ光の波長を５３２ｎｍとすることにより、レーザ
光が金属反射膜層で反射され、非晶質半導体光電変換層
に影響を及ぼさないようになる。また、局所的な加熱に
よる裏面電極層及び光電変換層への影響が抑えられる。 Here, the metal reflection film layer is made of silver , and the reflectance thereof is 90% or more in the region where the wavelength of the laser beam is 450 nm or more. Therefore, when removing the resist film,
By setting the wavelength of the laser light to 532 nm , the laser light is reflected by the metal reflection film layer and does not affect the amorphous semiconductor photoelectric conversion layer. In addition, the influence of local heating on the back electrode layer and the photoelectric conversion layer can be suppressed.

【００２０】本発明ではまた、絶縁表面を有する透光性
基板上に透明導電膜電極を設け、第1のスクライブによ
り前記透明導電膜電極を分割し、次に非晶質半導体光電
変換層を設け、第2のスクライブにより前記非晶質半導
体光電変換層を分割し、更に裏面電極層を設け、第3の
スクライブにより前記裏面電極層を分割する集積型薄膜
太陽電池の製造方法において、前記裏面電極層は酸化亜
鉛又はＩＴＯからなる透明導電膜と、アルミニウムから
なる金属反射膜層の2層を有し、前記第3のスクライブの
際、前記裏面電極層にレジストを塗布してレジスト膜を
設けた後に、前記非晶質半導体光電変換層に影響を及ぼ
さない、２６６ｎｍ、３０８ｎｍ又は５３２ｎｍのいず
れかのレーザ光の照射により前記レジスト膜を開溝除去
し、前記２層からなる裏面電極層をエッチング液（ＳＣ
１）を用いて溶解除去するものとする。In the present invention, a transparent conductive film electrode is provided on a transparent substrate having an insulating surface, the transparent conductive film electrode is divided by a first scribe, and then an amorphous semiconductor photoelectric conversion layer is provided. In the method for manufacturing an integrated thin-film solar cell, wherein the amorphous semiconductor photoelectric conversion layer is divided by a second scribe, a back electrode layer is further provided, and the back electrode layer is divided by a third scribe, the back electrode The layer has two layers of a transparent conductive film made of zinc oxide or ITO and a metal reflective film layer made of aluminum, and at the time of the third scribe, a resist was applied to the back electrode layer to form a resist film. Later, the amorphous semiconductor photoelectric conversion layer is affected.
No, the groove of the resist film is removed by irradiation with a laser beam of 266 nm, 308 nm, or 532 nm, and the back electrode layer composed of the two layers is etched with an etching solution (SC
It should be dissolved and removed using 1).

【００２１】これは、上記の方法を修飾して、銀に代え
てアルミニウムを金属反射膜層として用いるとともに、
レジスト膜の除去に用いるレーザ光の波長を変更したも
のである。レーザ光の波長が１００ｎｍ以上の領域で
は、アルミニウムの反射率は９０％以上となる。そのた
め、レジスト膜の除去の際、レーザ光の波長を２６６ｎ
ｍ、３０８ｎｍ又は５３２ｎｍとすることより、レーザ
光が金属反射膜層で反射され、非晶質半導体光電変換層
に影響を及ぼさないようになる。また、局所的な加熱に
よる裏面電極層及び光電変換層への影響が抑えられる。 This is a modification of the above method to replace silver.
Aluminum as a metal reflective film layer,
The wavelength of the laser beam used to remove the resist film was changed
Of. In the region where the wavelength of laser light is 100 nm or more, the reflectance of aluminum is 90% or more. Therefore, when removing the resist film, the wavelength of the laser beam is set to 266n.
By setting m, 308 nm or 532 nm , the laser light is reflected by the metal reflection film layer and does not affect the amorphous semiconductor photoelectric conversion layer. In addition, the influence of local heating on the back electrode layer and the photoelectric conversion layer can be suppressed.

【００２２】[0022]

【発明の実施の形態】DETAILED DESCRIPTION OF THE INVENTION

＜第１の実施形態＞本発明の第１の実施形態を図１及び
図２を用いて説明する。図１は本実施形態の製造方法に
より製造されたシングルセル構造の集積型薄膜太陽電池
の断面斜視図である。図２はその製造工程を示す断面図
である。尚、図１及び図２において、図４と同一の部分
については同一の符号を付してある。<First Embodiment> A first embodiment of the present invention will be described with reference to FIGS. FIG. 1 is a cross-sectional perspective view of an integrated type thin film solar cell having a single cell structure manufactured by the manufacturing method of this embodiment. FIG. 2 is a sectional view showing the manufacturing process. 1 and 2, the same parts as those in FIG. 4 are designated by the same reference numerals.

【００２３】図２（ａ）において、絶縁表面を有する透
光性基板１として、厚さ１mm、屈折率１．５のガラス基
板が使用される。図２（ｂ）に示すように、屈折率１．
５の酸化シリコン（ＳｉＯ2）２を１００ｎｍの厚さと
なるように、常圧ＣＶＤ法で基板１の温度を５００℃と
して積層する。In FIG. 2A, a glass substrate having a thickness of 1 mm and a refractive index of 1.5 is used as the transparent substrate 1 having an insulating surface. As shown in FIG. 2B, the refractive index is 1.
The silicon oxide (SiO 2 ) 5 of No. 5 is laminated at a temperature of the substrate 1 of 500 ° C. by the atmospheric pressure CVD method so as to have a thickness of 100 nm.

【００２４】更に、酸化シリコン（ＳｉＯ2）２の上
に、図２（ｃ）に示すように、透明導電膜層３を設け、
透明導電膜電極とする。透明導電膜層３は酸化スズ（Ｓ
ｎＯ2）でヘイズ率１２〜１５％のテクスチュア構造を
持ち１μｍの厚さとなるように常圧ＣＶＤ法で積層す
る。このとき、原料となるガスとして塩化スズ（ＳｎＣ
ｌ4）を２５０，０００sccm、ドーピングガスとしてフ
ッ化水素（ＨＦ）を１，０００sccm、酸化反応のために
水蒸気（Ｈ2Ｏ）を２００sccmでそれぞれ流す。Further, a transparent conductive film layer 3 is provided on the silicon oxide (SiO 2 ) 2 as shown in FIG. 2 (c).
It is used as a transparent conductive film electrode. The transparent conductive film layer 3 is made of tin oxide (S
nO 2 ) and has a texture structure with a haze ratio of 12 to 15%, and is laminated by atmospheric pressure CVD so as to have a thickness of 1 μm. At this time, tin chloride (SnC) is used as a raw material gas.
1 4 ) at 250,000 sccm, hydrogen fluoride (HF) at 1,000 sccm as a doping gas, and water vapor (H 2 O) at 200 sccm for the oxidation reaction.

【００２５】基板１の温度は５００℃で、透明導電膜層
３のシート抵抗は９Ω／□となる。これをレーザスクラ
イブ法やダイシング加工等により、図２（ｄ）に示すよ
うに短冊状のユニットセルに絶縁分割する。本実施形態
では、Ｎｄ：ＹＡＧレーザの基本波（波長１．０６μ
ｍ）のレーザ光１１を照射して、第１のスクライブライ
ンを開溝し、透明導電膜層３を絶縁分割加工する。The temperature of the substrate 1 is 500 ° C., and the sheet resistance of the transparent conductive film layer 3 is 9Ω / □. This is insulated and divided into strip-shaped unit cells as shown in FIG. 2D by a laser scribing method, a dicing process, or the like. In the present embodiment, the fundamental wave of the Nd: YAG laser (wavelength 1.06 μ
The laser light 11 of m) is irradiated to open the first scribe line, and the transparent conductive film layer 3 is subjected to insulation division processing.

【００２６】次に、図２（ｅ）に示すように、非晶質半
導体光電変換層４を積層する。光電変換層４の積層は、
まず、非晶質半導体のｐ層を１２ｎｍの厚さに積層す
る。この積層にはプラズマＣＶＤ装置（図示せず）が使
用される。基板１の温度を２００℃とし、反応ガスとし
てモノシランガス（ＳｉＨ4）を流量３０sccm、メタン
ガス（ＣＨ4）を流量８９sccm、水素ガス（Ｈ2）を流量
１５０sccmでそれぞれ流し、ドーピングガスとして１％
水素希釈のジボランガス（Ｂ2Ｈ6）を流量１０sccmで使
用する。Next, as shown in FIG. 2E, an amorphous semiconductor photoelectric conversion layer 4 is laminated. The stack of photoelectric conversion layers 4 is
First, a p-layer of an amorphous semiconductor is stacked to a thickness of 12 nm. A plasma CVD apparatus (not shown) is used for this stacking. The temperature of the substrate 1 was set to 200 ° C., a reaction gas of monosilane gas (SiH 4 ) at a flow rate of 30 sccm, a methane gas (CH 4 ) at a flow rate of 89 sccm, and a hydrogen gas (H 2 ) at a flow rate of 150 sccm, respectively, and 1% as a doping gas.
Diborane gas (B 2 H 6 ) diluted with hydrogen is used at a flow rate of 10 sccm.

【００２７】続いて、ｉ層を４００ｎｍの厚さとなるよ
うに前記プラズマＣＶＤ装置で積層する。このとき、前
記プラズマＣＶＤ装置において基板１の温度を２００℃
に保持し、反応ガスとしてモノシランガス（ＳｉＨ4）
を流量６０sccm、水素ガスを流量２０sccmで流す。Subsequently, the i layer is laminated by the plasma CVD device so as to have a thickness of 400 nm. At this time, the temperature of the substrate 1 is set to 200 ° C. in the plasma CVD apparatus.
Held as a monosilane gas (SiH 4 ) as a reaction gas
At a flow rate of 60 sccm and hydrogen gas at a flow rate of 20 sccm.

【００２８】更に、ｎ層を１００ｎｍの厚さとなるよう
に前記プラズマＣＶＤ装置で積層する。このとき、前記
プラズマＣＶＤ装置において基板１の温度を２００℃に
保持し、反応ガスとしてモノシランガス（ＳｉＨ4）を
流量６０sccm、水素ガス（Ｈ2）を流量３sccm、ドーピ
ングガスとして０．３％水素（Ｈ2）希釈のホスフィン
ガス（ＰＨ3）を流量１８sccmで流す。このようにし
て、図２（ｅ）に示すように、非晶質半導体光電変換層
４が設けられる。Further, the n layer is laminated by the plasma CVD apparatus so as to have a thickness of 100 nm. At this time, in the plasma CVD apparatus, the temperature of the substrate 1 is maintained at 200 ° C., the reaction gas is monosilane gas (SiH 4 ) at a flow rate of 60 sccm, the hydrogen gas (H 2 ) is at a flow rate of 3 sccm, and the doping gas is 0.3% hydrogen ( A phosphine gas (PH 3 ) diluted with H 2 ) is flown at a flow rate of 18 sccm. In this way, the amorphous semiconductor photoelectric conversion layer 4 is provided as shown in FIG.

【００２９】その後、図２（ｆ）に示すように、第１の
スクライブラインと近接した位置に第１のスクライブラ
インと平行となるように、レーザ光１２を照射して、非
晶質半導体光電変換層４を第２のスクライブにより分割
加工する。尚、照射するレーザ光１２は、Ｎｄ：ＹＡＧ
レーザ、エキシマレーザのいずれでもよいが、保守の容
易さや維持費の低さ等から、Ｎｄ：ＹＡＧレーザが工業
的に優位であると考えられる。本実施形態では、Ｎｄ：
ＹＡＧレーザの第２高調波（ＳＨＧ、波長０．５３２μ
ｍ）のレーザ光１２を照射して第２のスクライブライン
を開溝し、非晶質半導体光電変換層４の分割加工を行
う。Then, as shown in FIG. 2 (f), laser light 12 is irradiated to a position close to the first scribe line so as to be parallel to the first scribe line, and the amorphous semiconductor photoelectric cell is irradiated. The conversion layer 4 is divided and processed by the second scribe. The laser light 12 to be applied is Nd: YAG.
Although either a laser or an excimer laser may be used, the Nd: YAG laser is considered to be industrially superior because of its ease of maintenance and low maintenance cost. In this embodiment, Nd:
Second harmonic of YAG laser (SHG, wavelength 0.532μ
The second scribe line is opened by irradiating the laser beam 12 of m) to divide the amorphous semiconductor photoelectric conversion layer 4.

【００３０】次に、図２（ｇ）に示すように、透明導電
膜層５として酸化亜鉛（ＺｎＯ）を５０ｎｍの厚さとな
るようにスパッタリング法によって積層する。尚、透明
導電膜層５にはＩＴＯ（酸化インジウムと酸化スズの混
合物）を使用することも可能である。そして、図２
（ｈ）に示すように、裏面金属反射膜層６として銀（Ａ
ｇ）を５００ｎｍの厚さとなるようにスパッタリング法
によって積層する。裏面金属反射膜層６で光が反射して
光電変換層４に照射するようになり、光の有効利用が図
られる。このように、裏面電極層は透明導電膜層５と裏
面金属反射膜層６から成る。Next, as shown in FIG. 2G, zinc oxide (ZnO) is deposited as the transparent conductive film layer 5 by a sputtering method so as to have a thickness of 50 nm. It should be noted that ITO (a mixture of indium oxide and tin oxide) can be used for the transparent conductive film layer 5. And FIG.
As shown in (h), silver (A
g) is laminated by a sputtering method so as to have a thickness of 500 nm. Light is reflected by the back surface metal reflective film layer 6 to irradiate the photoelectric conversion layer 4, and the light can be effectively used. Thus, the back electrode layer is composed of the transparent conductive film layer 5 and the back metal reflection film layer 6.

【００３１】尚、酸化亜鉛（ＺｎＯ）と銀（Ａｇ）の積
層は、スパッタリング法に限定されるものではなく、例
えば蒸着法によってそれぞれ積層することも可能であ
り、また一方をスパッタリング法で他方を蒸着法で積層
することも可能である。The stacking of zinc oxide (ZnO) and silver (Ag) is not limited to the sputtering method, and it is also possible to stack each by, for example, the vapor deposition method. It is also possible to stack them by a vapor deposition method.

【００３２】次に、第３のスクライブを行う。まず、図
２（ｉ）に示すように、レジスト膜７が設けられる。
尚、レジスト膜７には耐酸、耐アルカリ性のあるレジス
トが使用され、例えば石油ピッチ系メッキレジストが使
用される。スクリーン印刷で非晶質半導体光電変換層４
に物理的なダメージを与えない条件で、基板１の金属反
射膜層６が設けられた面の全面に４０μｍの厚さとなる
ようにレジストを塗布する。Next, a third scribe is performed. First, as shown in FIG. 2I, a resist film 7 is provided.
A resist having acid resistance and alkali resistance is used for the resist film 7, for example, a petroleum pitch plating resist is used. Amorphous semiconductor photoelectric conversion layer 4 by screen printing
A resist is applied to the entire surface of the substrate 1 on which the metal reflective film layer 6 is provided so as to have a thickness of 40 μm under the condition that physical damage is not given to the substrate.

【００３３】スクリーン印刷では非晶質光電変換層４へ
物理的ダメージを与え、リークの発生や変換効率の低下
の原因となるという欠点があるので、レジストの塗布に
スプレー法やスピンコート法を使用することも可能であ
る。この場合には、レジスト膜７の塗厚がこれより薄く
なる。また、レジストの粘度は、スクリーン印刷の場合
には1,000〜100,000cP程度の粘度が必要となるが、スプ
レー印刷法やスピンコート法を用いる場合には、更に低
粘度のレジストを使用する必要がある。Screen printing has a drawback that it causes physical damage to the amorphous photoelectric conversion layer 4, causing leaks and lowering conversion efficiency. Therefore, a spray method or a spin coating method is used for coating the resist. It is also possible to do so. In this case, the coating thickness of the resist film 7 becomes thinner than this. In addition, the viscosity of the resist requires a viscosity of about 1,000 to 100,000 cP in the case of screen printing, but in the case of using the spray printing method or spin coating method, it is necessary to use a resist with a lower viscosity. .

【００３４】そして、図２（ｊ）に示すように、第１の
スクライブラインと反対側で、第２のスクライブライン
と近接した位置で、Ｑスイッチ発振Ｎｄ：ＹＡＧレーザ
の第２高調波（ＳＨＧ、波長０．５３２μｍ）のレーザ
光１３をレジスト膜７の膜面から発振周波数５ｋＨｚ、
レーザ照射スピード４０mm／sec、加工面出力１５０Ｗ
／mm2で照射し、レジスト膜７のみを開溝除去する。
尚、スプレー法やスピンコート法を使用してレジスト膜
７を設けた場合、膜厚が異なるので、レーザ光１３の照
射条件が異なる。Then, as shown in FIG. 2 (j), at the position opposite to the first scribe line and close to the second scribe line, the second harmonic (SHG) of the Q-switch oscillation Nd: YAG laser is generated. , A wavelength of 0.532 μm) from the film surface of the resist film 7 with an oscillation frequency of 5 kHz,
Laser irradiation speed 40 mm / sec, processing surface output 150 W
Irradiation is performed at / mm 2 , and only the resist film 7 is opened and removed.
When the resist film 7 is formed by using the spray method or the spin coating method, the film thickness is different, and thus the irradiation condition of the laser beam 13 is different.

【００３５】また、レーザ光１３の波長を４５０ｎｍ以
上とすることにより、裏面金属反射膜層６でレーザ光１
３の反射率が９０％以上となる。そのため、レーザ光１
３が裏面金属反射膜層６で反射され光電変換層４に影響
が及びにくくなる。また、局所的な熱加熱による裏面金
属反射膜層６及び光電変換層４への影響が抑えられる。Further, by setting the wavelength of the laser beam 13 to 450 nm or more, the laser beam 1 is reflected by the back surface metal reflection film layer 6.
The reflectance of No. 3 is 90% or more. Therefore, laser light 1
3 is reflected by the back surface metal reflection film layer 6 and the photoelectric conversion layer 4 is less affected. Moreover, the influence on the back surface metal reflection film layer 6 and the photoelectric conversion layer 4 due to local heat heating is suppressed.

【００３６】その後、３１％過酸化水素水：３０％アン
モニア水：水（体積比１：１：１０）のエッチング液
（ＳＣ１）で、酸化亜鉛（ＺｎＯ）の透明導電膜層５と
銀（Ａｇ）の裏面金属反射膜層６を溶解除去する。これ
により、図２（ｋ）に示すように、第３のスクライブラ
インを形成してパターニングを施す。このようにユニッ
トセルに分割され、図１に示すようにユニットセルが直
列に接続されたシングルセル構造の集積型薄膜太陽電池
となる。尚、図１において図２と同一の部分については
同一の符号を付し、説明を省略する。Thereafter, the transparent conductive film layer 5 made of zinc oxide (ZnO) and the silver (Ag) were formed by using an etching solution (SC1) of 31% hydrogen peroxide water: 30% ammonia water: water (volume ratio 1: 1: 10). The rear surface metal reflection film layer 6 of 4) is dissolved and removed. As a result, as shown in FIG. 2K, the third scribe line is formed and patterned. In this way, the integrated thin-film solar cell having a single cell structure is obtained in which the unit cells are divided and the unit cells are connected in series as shown in FIG. In FIG. 1, the same parts as those in FIG. 2 are designated by the same reference numerals and the description thereof will be omitted.

【００３７】本実施形態により作製された３００mm×３
００mmサイズの集積型薄膜太陽電池の特性は、ＡＭ１．
５（１００ｍＷ／ｃｍ2）において、短絡電流が０．５
２２Ａ、開放電圧が２６．４Ｖ、曲線因子が０．７２、
変換効率が１１％であった。300 mm × 3 manufactured by this embodiment
The characteristics of the integrated thin-film solar cell of 00 mm size are AM1.
5 (100 mW / cm 2 ), the short-circuit current was 0.5
22A, open-circuit voltage 26.4V, fill factor 0.72,
The conversion efficiency was 11%.

【００３８】尚、レジストの塗布には、スクリーン印刷
法以外に、スプレー法やスピンコート法等も使用できる
ので、レジスト膜７の膜厚を薄くすることができる。こ
れにより、製造に使用されるレジストの量を減らすこと
ができる。また、裏面電極層５、６の分割加工後にレジ
スト膜７を剥離する場合、レジスト膜７を溶解するため
に必要な有機溶剤等の使用量を抑えることが可能とな
る。そのため、製造コストが低減され、廃液処理等の負
担が軽減できる。また、環境に対する影響を抑制するこ
とができる。In addition to the screen printing method, a spray method, a spin coating method, or the like can be used to apply the resist, so that the thickness of the resist film 7 can be reduced. As a result, the amount of resist used for manufacturing can be reduced. Further, when the resist film 7 is peeled off after the back electrode layers 5 and 6 are divided, it is possible to suppress the amount of the organic solvent or the like used to dissolve the resist film 7. Therefore, the manufacturing cost can be reduced, and the burden of waste liquid treatment and the like can be reduced. Moreover, the influence on the environment can be suppressed.

【００３９】本実施形態では、非晶質半導体材料に非晶
質シリコン（a-Si:H）が使用されていたが、非晶質シリ
コンゲルマニウム（a-SiGe:H）、非晶質シリコンカーバ
イド（a-SiC:H）や非晶質シリコンスズ（a-SiSn:H）等
の非晶質シリコン系の半導体も使用できる。これらをｐ
ｉｎ構造とすることにより比較的良好な特性が得られ
る。In this embodiment, amorphous silicon (a-Si: H) is used as the amorphous semiconductor material, but amorphous silicon germanium (a-SiGe: H) and amorphous silicon carbide are used. Amorphous silicon semiconductors such as (a-SiC: H) and amorphous silicon tin (a-SiSn: H) can also be used. P these
With the in structure, relatively good characteristics can be obtained.

【００４０】＜第２の実施形態＞本発明の第２の実施形
態を図３を用いて説明する。絶縁表面を有する透光性基
板１として、上記第１の実施形態と同様に強化ガラス基
板を使用する。図３（ａ）に示すように、基板１に酸化
シリコン（ＳｉＯ2）膜２と酸化スズ（ＳｎＯ2）の透明
導電膜層３を上記第１の実施形態と同様に積層し、レー
ザ光１１による第１のスクライブを行う。尚、図３にお
いて図２と同一の部分については同一の符号を付してあ
る。<Second Embodiment> A second embodiment of the present invention will be described with reference to FIG. As the transparent substrate 1 having an insulating surface, a tempered glass substrate is used as in the first embodiment. As shown in FIG. 3A, a silicon oxide (SiO 2 ) film 2 and a transparent conductive film layer 3 of tin oxide (SnO 2 ) are laminated on a substrate 1 in the same manner as in the first embodiment, and laser light 11 Perform the first scribe by. In FIG. 3, the same parts as those in FIG. 2 are designated by the same reference numerals.

【００４１】次に、図３（ｂ）に示すように、第１段目
の非晶質半導体光電変換層８を積層する。まず、ｐ層を
１０ｎｍの厚さとなるように積層する。この積層にはプ
ラズマＣＶＤ装置（図示せず）が使用される。基板１の
温度を２００℃とし、反応ガスにはモノシランガス（Ｓ
ｉＨ4）を流量３０sccm、メタンガス（ＣＨ4）を流量３
５．６sccm、水素ガス（Ｈ2）を流量１６０sccmで流
し、ドーピングガスとして０．６％水素希釈のジボラン
ガス（Ｂ2Ｈ6）を流量０．０６sccmで使用する。このと
きの反応圧力は０．３２Torrである。Next, as shown in FIG. 3B, the first-stage amorphous semiconductor photoelectric conversion layer 8 is laminated. First, the p layer is laminated to have a thickness of 10 nm. A plasma CVD apparatus (not shown) is used for this stacking. The temperature of the substrate 1 is set to 200 ° C., and the reaction gas is monosilane gas (S
iH 4 ) flow rate 30 sccm, methane gas (CH 4 ) flow rate 3
5.6 sccm, hydrogen gas (H 2 ) is flown at a flow rate of 160 sccm, and diborane gas (B 2 H 6 ) diluted with 0.6% hydrogen is used as a doping gas at a flow rate of 0.06 sccm. The reaction pressure at this time is 0.32 Torr.

【００４２】続いて、ｉ層を１３０ｎｍの厚さとなるよ
うに積層する。このとき、上記プラズマＣＶＤ装置にお
いて基板１の温度は２００℃で保持し、反応圧力は０．
１２Torrである。反応ガスとしてモノシランガス（Ｓｉ
Ｈ4）を流量６０sccm、水素ガス（Ｈ2）を流量２０sccm
で流す。Subsequently, the i layer is laminated to have a thickness of 130 nm. At this time, in the plasma CVD apparatus, the temperature of the substrate 1 is maintained at 200 ° C., and the reaction pressure is 0.
It is 12 Torr. Monosilane gas (Si
H 4 ) flow rate 60 sccm, hydrogen gas (H 2 ) flow rate 20 sccm
Flush with.

【００４３】更に、ｎ層を１００ｎｍの厚さとなるよう
に積層する。上記プラズマＣＶＤ装置において基板１の
温度を２００℃に保持し、反応ガスとしてモノシランガ
ス（ＳｉＨ4）を流量６０sccm、水素ガス（Ｈ2）を流量
２０sccm、ドーピングガスは２％水素希釈ホスフィンガ
ス（ＰＨ3）を流量０．３５sccmで流す。このようにし
て、第１段目の非晶質半導体光電変換層８を積層する。Further, n layers are laminated so as to have a thickness of 100 nm. In the plasma CVD apparatus, the temperature of the substrate 1 is maintained at 200 ° C., the reaction gas is monosilane gas (SiH 4 ) at a flow rate of 60 sccm, hydrogen gas (H 2 ) is at a flow rate of 20 sccm, and the doping gas is 2% hydrogen-diluted phosphine gas (PH 3 ) At a flow rate of 0.35 sccm. In this way, the first-stage amorphous semiconductor photoelectric conversion layer 8 is laminated.

【００４４】次に、図３（ｃ）に示すように、第２段目
の非晶質半導体光電変換層９を積層する。このとき、第
２段目の非晶質半導体光電変換層９において、ｐ層とｉ
層を第１段目の非晶質半導体光電変換層８での積層と同
じ条件でｐ層、ｉ層の順に積層する。その後、ｎ層を１
００ｎｍの厚さとなるように積層する。Next, as shown in FIG. 3C, a second-stage amorphous semiconductor photoelectric conversion layer 9 is laminated. At this time, in the amorphous semiconductor photoelectric conversion layer 9 of the second stage,
The layers are stacked in the order of p-layer and i-layer under the same conditions as the stacking in the first-stage amorphous semiconductor photoelectric conversion layer 8. Then, n layer 1
The layers are laminated to have a thickness of 00 nm.

【００４５】ｎ層の積層には、反応ガスとしてモノシラ
ンガス（ＳｉＨ4）を流量３０sccm、水素ガス（Ｈ2）を
流量１６０sccm、ドーピングガスは０．６％水素希釈の
ホスフィンガス（ＰＨ3）を流量１０sccmで流す。この
ときの反応圧力は０．３２Torrである。このようにし
て、第２段目の非晶質半導体光電変換層９を積層する。For stacking n layers, a reaction gas of monosilane gas (SiH 4 ) at a flow rate of 30 sccm, hydrogen gas (H 2 ) at a flow rate of 160 sccm, and doping gas at a flow rate of phosphine gas (PH 3 ) diluted with 0.6% hydrogen. Run at 10 sccm. The reaction pressure at this time is 0.32 Torr. In this way, the second-stage amorphous semiconductor photoelectric conversion layer 9 is laminated.

【００４６】次に、図３（ｄ）に示すように、レーザ光
１２の照射により第２のスクライブを行う。これによ
り、第１段目及び第２段目の非晶質半導体光電変換層
８、９を所定のセルに分割する。そして、図３（ｅ）に
示すように、透明導電膜層５及び裏面金属反射膜層６を
設ける。上記第１の実施形態と同様に、レジストを裏面
金属反射膜層６の設けられた面に全面塗布してレジスト
膜７を設け、レジスト膜７をレーザ光によりパターニン
グを行った後に、エッチング液（ＳＣ１）により透明導
電膜層５と裏面金属反射膜層６を溶解除去する。このよ
うに、第３のスクライブを行う。Next, as shown in FIG. 3D, a second scribe is performed by irradiation with the laser beam 12. As a result, the first-stage and second-stage amorphous semiconductor photoelectric conversion layers 8 and 9 are divided into predetermined cells. Then, as shown in FIG. 3E, the transparent conductive film layer 5 and the back surface metal reflective film layer 6 are provided. Similar to the first embodiment, a resist is applied to the entire surface on which the back surface metal reflection film layer 6 is provided to provide a resist film 7, and the resist film 7 is patterned by laser light, and then an etching solution ( The transparent conductive film layer 5 and the back surface metal reflective film layer 6 are dissolved and removed by SC1). In this way, the third scribe is performed.

【００４７】このように作製された２段タンデム構造の
３００mm×３００mmサイズの集積型薄膜太陽電池の特性
は、ＡＭ１．５（１００ｍＷ／ｃｍ2）において、短絡
電流が０．３０９Ａ、開放電圧が４４．４Ｖ、曲線因子
が０．７２、変換効率が１１％であった。The characteristics of the integrated thin-film solar cell of 300 mm × 300 mm size of the two-stage tandem structure manufactured as described above are that the short-circuit current is 0.309 A and the open-circuit voltage is 44 at AM1.5 (100 mW / cm 2 ). The value was 0.4 V, the fill factor was 0.72, and the conversion efficiency was 11%.

【００４８】＜第３の実施形態＞本発明の第３の実施形
態を図２を用いて説明する。本実施形態では上記第１の
実施形態とほぼ同様となっている。図２（ａ）〜（ｇ）
に示す製造の工程は上記第１の実施形態と同様であり、
説明を省略する。ただし、図２（ｈ）において、裏面金
属反射膜層６にはアルミニウム（Ａｌ）が使用される。
その後、図２（ｉ）に示すように石油ピッチ系メッキレ
ジスト膜７がスクリーン印刷で４０μｍの厚さとなるよ
うに設けられる。<Third Embodiment> A third embodiment of the present invention will be described with reference to FIG. The present embodiment is almost the same as the first embodiment. 2 (a) to (g)
The manufacturing process shown in is similar to that of the first embodiment,
The description is omitted. However, in FIG. 2H, aluminum (Al) is used for the back surface metal reflective film layer 6.
Thereafter, as shown in FIG. 2I, a petroleum pitch-based plating resist film 7 is provided by screen printing so as to have a thickness of 40 μm.

【００４９】そして、図２（ｊ）に示すようにＱスイッ
チ発振Ｎｄ：ＹＡＧレーザの第２高調波（ＳＨＧ、波長
０．５３２μｍ）のレーザ光１３をレジスト膜７の膜面
から発振周波数５ｋＨｚ、レーザ照射スピード４０mm／
sec、加工面出力１５０Ｗ／mm2で照射し、レジスト膜７
のみを開溝除去する。そして、図２（ｋ）に示すよう
に、前述したエッチング液（ＳＣ１）を使用して、裏面
電極層５、６を溶解除去する。尚、レジストの塗布にス
プレー印刷法やスピンコート法を使用した場合、レジス
ト膜７の塗厚がスクリーン印刷法を使用したときより薄
くなるため、レーザ光１３の照射条件が異なる。Then, as shown in FIG. 2 (j), the laser light 13 of the second harmonic (SHG, wavelength 0.532 μm) of the Q-switch oscillation Nd: YAG laser is emitted from the film surface of the resist film 7 at an oscillation frequency of 5 kHz. Laser irradiation speed 40 mm /
Irradiate for sec, processing surface output 150 W / mm 2 , resist film 7
Remove only the groove. Then, as shown in FIG. 2K, the back surface electrode layers 5 and 6 are dissolved and removed by using the above-described etching solution (SC1). When the spray printing method or the spin coating method is used to apply the resist, the coating thickness of the resist film 7 becomes thinner than when the screen printing method is used, and thus the irradiation conditions of the laser beam 13 are different.

【００５０】本実施形態では、レジスト膜７の開溝除去
にはＮｄ：ＹＡＧレーザのＳＨＧ波を使用したが、波長
１００ｎｍ以上であれば、アルミニウム（Ａｌ）の反射
率が９０％以上となるので、レジスト膜７の開溝除去の
際に光電変換層４にレーザ光１３の照射が防止される。
例えば、Ｎｄ：ＹＡＧレーザの第４高調波（ＦＨＧ、波
長０．２６６μｍ）やエキシマレーザ（例えば、ＸｅＣ
ｌ、波長０．３０８μｍ）等を使用することができる。
ただし、前述したように、保守の容易さや維持費の低さ
等の点から、Ｎｄ：ＹＡＧレーザが工業的に優位である
と考えられる。In the present embodiment, the SHG wave of the Nd: YAG laser was used to remove the open groove of the resist film 7. However, if the wavelength is 100 nm or more, the reflectance of aluminum (Al) becomes 90% or more. Irradiation of the laser beam 13 to the photoelectric conversion layer 4 is prevented when the open groove of the resist film 7 is removed.
For example, a fourth harmonic (FHG, wavelength 0.266 μm) of an Nd: YAG laser or an excimer laser (for example, XeC
1, wavelength 0.308 μm) or the like can be used.
However, as described above, the Nd: YAG laser is considered to be industrially superior in terms of ease of maintenance and low maintenance cost.

【００５１】また、上記第２の実施形態（図３）に示す
ように第１段目及び第２段目の非晶質半導体光電変換層
８、９を設けたタンデム構造としても、裏面金属反射膜
層６をアルミニウム（Ａｌ）とすることができる。Also, as shown in the second embodiment (FIG. 3), the tandem structure in which the amorphous semiconductor photoelectric conversion layers 8 and 9 of the first stage and the second stage are provided also has a back surface metal reflection. The film layer 6 can be aluminum (Al).

【００５２】＜第４の実施形態＞本発明の第４の実施形
態を説明する。絶縁表面を有する透光製基板として、厚
さ１mm、屈折率１．５のガラス基板を使用する。基板の
表面にサンドブラスト加工を施してテクスチュア構造を
形成する。そして、基板に透明導電膜層として酸化亜鉛
（ＺｎＯ）を３００ｎｍの厚さとなるようにスパッタリ
ング法により積層する。<Fourth Embodiment> A fourth embodiment of the present invention will be described. A glass substrate having a thickness of 1 mm and a refractive index of 1.5 is used as a transparent substrate having an insulating surface. The surface of the substrate is sandblasted to form a textured structure. Then, zinc oxide (ZnO) is laminated as a transparent conductive film layer on the substrate by a sputtering method so as to have a thickness of 300 nm.

【００５３】尚、透明導電膜層の形成はスパッタリング
法に限らず、例えばＭＯＣＶＤ法やゾルゲル法等でもよ
い。その後、シングルセル構造とするときは上記第１の
実施形態の該当する部分で同様に製造でき、一方、タン
デム構造とするときは上記第２の実施形態の該当する部
分で同様に製造できるので説明を省略する。The formation of the transparent conductive film layer is not limited to the sputtering method, but may be the MOCVD method or the sol-gel method. After that, a single cell structure can be manufactured in the same manner in the corresponding portions of the first embodiment, while a tandem structure can be manufactured in the same manner in the corresponding portions in the second embodiment. Is omitted.

【００５４】ガラス基板にテクスチュア加工が施される
ことにより、入射した光が散乱され、光電変換層を通過
する光の光路長が大きくなり、薄膜太陽電池の変換効率
が向上する。By subjecting the glass substrate to the texture processing, the incident light is scattered, the optical path length of the light passing through the photoelectric conversion layer is increased, and the conversion efficiency of the thin film solar cell is improved.

【００５５】[0055]

【発明の効果】裏面電極層を酸化亜鉛又はＩＴＯからな
る透明導電膜と銀からなる金属反射膜層の２層とし、第
３のスクライブの際、裏面電極層にレジストを塗布して
レジスト膜を設けた後に、波長５３２ｎｍのレーザ光の
照射によりレジスト膜を開溝除去し、２層からなる裏面
電極層をエッチング液（ＳＣ１）を用いて溶解除去する
ようにした本発明の集積型薄膜太陽電池の製造方法で
は、次の効果が得られる。すなわち、レーザ光の照射で
は高精度の加工が行えるので、小さな溝幅で裏面電極層
を分割することができる。これにより、集積モジュール
全体の発電有効面積損失が低減できる。また、裏面電極
をエッチング液により溶解除去することにより、非晶質
半導体光電変換層にダメージを与えることなく確実に分
割が行える。そのため、シャント抵抗が低下せず、非晶
質半導体光電変換層の膜質の低下要因が排除される。さ
らに、裏面電極層を２層構造とし、レジスト膜の開溝除
去に用いるレーザの波長と金属反射膜の材料を、高い反
射率となるように設定しているため、裏面電極層及び光
電変換層へのレーザの影響が抑えられて、発電有効面積
の損失防止と光電変換層の膜質の低下防止を確実に実現
できる。したがって、集積型太陽電池の特性及び歩留ま
りが向上する。The back electrode layer is made of zinc oxide or ITO.
And a metal reflective film layer made of silver.
At the time of scribing in 3, apply resist to the back electrode layer
After providing the resist film,
The resist film is opened to remove the groove by irradiation, and the back surface consists of two layers.
Dissolve and remove the electrode layer using an etching solution (SC1)
In the method for manufacturing an integrated thin-film solar cell of the present invention,
Has the following effects. That is, by irradiation with laser light
Since it performs the machining of high precision, the back electrode layer with a small groove width
Can be split . Thereby, the power generation effective area loss of the entire integrated module can be reduced. Also, the back electrode
The by dissolving removed by etching solution, it can be performed reliably divide without damaging the amorphous semiconductor photoelectric conversion layer. Therefore, the shunt resistance does not decrease, and the factor that deteriorates the film quality of the amorphous semiconductor photoelectric conversion layer is eliminated. It
In addition, the back electrode layer has a two-layer structure, and the trenches in the resist film are removed.
The wavelength of the laser used for the
Since the emissivity is set, the back electrode layer and light
The influence of the laser on the electric conversion layer is suppressed and the effective power generation area is reduced.
Surely prevents loss of light and prevents deterioration of the quality of the photoelectric conversion layer
it can. Therefore , the characteristics and yield of the integrated solar cell are improved.

【００５６】裏面電極層を酸化亜鉛又はＩＴＯからなる
透明導電膜とアルミニウムからなる金属反射膜層の２層
とし、第３のスクライブの際、裏面電極層にレジストを
塗布してレジスト膜を設けた後に、波長２６６ｎｍ、３
０８ｎｍ又は５３２ｎｍのいずれかのレーザ光の照射に
よりレジスト膜を開溝除去し、２層からなる裏面電極層
をエッチング液（ＳＣ１）を用いて溶解除去するように
した本発明の集積型薄膜太陽電池の製造方法でも、上記
と同様の効果が得られる。 The back electrode layer is made of zinc oxide or ITO
Two layers of transparent conductive film and metal reflective film layer made of aluminum
Then, at the time of the third scribe, a resist is applied to the back electrode layer.
After coating and providing a resist film, the wavelength of 266 nm, 3
For irradiation with either 08 nm or 532 nm laser light
The resist film is opened to remove the groove, and the back electrode layer is composed of two layers.
So that it is dissolved and removed using an etching solution (SC1)
Also in the method for manufacturing an integrated thin-film solar cell of the present invention,
The same effect as can be obtained.

【００５７】[0057]

【００５８】[0058]

【００５９】[0059]

【図面の簡単な説明】[Brief description of drawings]

【図１】 本発明の第１の実施形態による集積型薄膜太
陽電池の断面斜視図。FIG. 1 is a cross-sectional perspective view of an integrated type thin film solar cell according to a first embodiment of the present invention.

【図２】 その製造工程を示す断面図。FIG. 2 is a cross-sectional view showing the manufacturing process thereof.

【図３】 本発明の第２の実施形態の製造工程を示す断
面図。FIG. 3 is a cross-sectional view showing the manufacturing process of the second embodiment of the present invention.

【図４】 従来の集積型薄膜太陽電池の製造工程を示す
断面図。FIG. 4 is a cross-sectional view showing a manufacturing process of a conventional integrated thin-film solar cell.

【符号の説明】[Explanation of symbols]

１ 透光性絶縁基板 ２ ＳｉＯ2 ３ 表面透明導電膜層 ４ 非晶質半導体光電変換層 ５ 裏面透明導電膜層 ６ 裏面金属反射膜層 ７ レジスト膜 ８ 第１段目非晶質半導体光電変換層 ９ 第２段目非晶質半導体光電変換層 １０ 裏面電極層 １１ レーザ光（第１パターニング） １２ レーザ光（第２パターニング） １３ レーザ光（第３パターニング）1 Transparent Insulating Substrate 2 SiO 2 3 Surface Transparent Conductive Conductive Layer 4 Amorphous Semiconductor Photoelectric Conversion Layer 5 Back Transparent Conductive Conductive Layer 6 Back Metal Reflective Film Layer 7 Resist Film 8 First Stage Amorphous Semiconductor Photoelectric Conversion Layer 9 Second Stage Amorphous Semiconductor Photoelectric Conversion Layer 10 Back Electrode Layer 11 Laser Light (First Patterning) 12 Laser Light (Second Patterning) 13 Laser Light (Third Patterning)

───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平５−183178（ＪＰ，Ａ) 特開 昭61−187379（ＪＰ，Ａ) 特開 昭62−54479（ＪＰ，Ａ)   ─────────────────────────────────────────────────── ─── Continued front page       (56) Reference JP-A-5-183178 (JP, A)                 JP-A-61-187379 (JP, A)                 JP 62-54479 (JP, A)

Claims (2)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】 絶縁表面を有する透光性基板上に透明導
電膜電極を設け、第1のスクライブにより前記透明導電
膜電極を分割し、次に非晶質半導体光電変換層を設け、
第2のスクライブにより前記非晶質半導体光電変換層を
分割し、更に裏面電極層を設け、第3のスクライブによ
り前記裏面電極層を分割する集積型薄膜太陽電池の製造
方法において、 前記裏面電極層は酸化亜鉛又はＩＴＯからなる透明導電
膜と、銀からなる金属反射膜層の２層からなり、前記第
3のスクライブの際、前記裏面電極層にレジストを塗布
してレジスト膜を設けた後に、前記非晶質半導体光電変
換層に影響を及ぼさない、波長５３２ｎｍのレーザ光照
射により前記レジスト膜を開溝除去し、前記２層からな
る裏面電極層をエッチング液（ＳＣ１）を用いて溶解除
去することを特徴とする集積型薄膜太陽電池の製造方
法。1. A transparent conductive film electrode is provided on a transparent substrate having an insulating surface, the transparent conductive film electrode is divided by a first scribe, and then an amorphous semiconductor photoelectric conversion layer is provided.
In the method for manufacturing an integrated thin-film solar cell, wherein the amorphous semiconductor photoelectric conversion layer is divided by a second scribe, a back electrode layer is further provided, and the back electrode layer is divided by a third scribe, the back electrode layer Is a transparent conductive film made of zinc oxide or ITO and a metal reflective film layer made of silver.
At the time of scribing in 3, after applying a resist to the back electrode layer to form a resist film, the amorphous semiconductor photoelectric conversion film is formed.
An integration characterized in that the groove of the resist film is removed by irradiation with a laser beam having a wavelength of 532 nm and the back electrode layer consisting of the two layers is dissolved and removed using an etching solution (SC1), which does not affect the replacement layer. -Type thin film solar cell manufacturing method. 【請求項２】 絶縁表面を有する透光性基板上に透明導
電膜電極を設け、第1のスクライブにより前記透明導電
膜電極を分割し、次に非晶質半導体光電変換層を設け、
第2のスクライブにより前記非晶質半導体光電変換層を
分割し、更に裏面電極層を設け、第3のスクライブによ
り前記裏面電極層を分割する集積型薄膜太陽電池の製造
方法において、 前記裏面電極層は酸化亜鉛又はＩＴＯからなる透明導電
膜と、アルミニウムからなる金属反射膜層の2層を有
し、前記第3のスクライブの際、前記裏面電極層にレジ
ストを塗布してレジスト膜を設けた後に、前記非晶質半
導体光電変換層に影響を及ぼさない、２６６ｎｍ、３０
８ｎｍ又は５３２ｎｍのいずれかのレーザ光の照射によ
り前記レジスト膜を開溝除去し、前記２層からなる裏面
電極層をエッチング液（ＳＣ１）を用いて溶解除去する
ことを特徴とする集積型太陽電池の製造方法。2. A transparent conductive film electrode is provided on a transparent substrate having an insulating surface, the transparent conductive film electrode is divided by a first scribe, and then an amorphous semiconductor photoelectric conversion layer is provided.
In the method for manufacturing an integrated thin-film solar cell, wherein the amorphous semiconductor photoelectric conversion layer is divided by a second scribe, a back electrode layer is further provided, and the back electrode layer is divided by a third scribe, the back electrode layer Has two layers of a transparent conductive film made of zinc oxide or ITO and a metal reflective film layer made of aluminum. After the third scribe, after applying a resist to the back electrode layer to form a resist film, , The amorphous half
266 nm, which does not affect the conductor photoelectric conversion layer , 30
An integrated solar cell, characterized in that the resist film is opened by irradiation with a laser beam of either 8 nm or 532 nm, and the back electrode layer consisting of the two layers is dissolved and removed by using an etching solution (SC1). Manufacturing method.
JP22347296A 1996-08-26 1996-08-26 Manufacturing method of integrated thin-film solar cell Expired - Fee Related JP3510740B2 (en)

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US08/917,105 US5956572A (en) 1996-08-26 1997-08-25 Method of fabricating integrated thin film solar cells
EP97306507A EP0827212B1 (en) 1996-08-26 1997-08-26 Method of fabricating integrated thin film solar cells
DE69734860T DE69734860T2 (en) 1996-08-26 1997-08-26 Manufacturing process of integrated thin-film solar cells

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EP0827212B1 (en) 2005-12-14
DE69734860T2 (en) 2006-08-17
EP0827212A3 (en) 1999-08-18
DE69734860D1 (en) 2006-01-19
JPH1070295A (en) 1998-03-10
EP0827212A2 (en) 1998-03-04

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